Ici thickener composition and uses

ABSTRACT

A viscosity regulating composition and its method of manufacture. The composition comprises a mixture of (a) a branched polymer having the formula [M]-[(A1O)-L1-(A1O)—R1]n, wherein M is polybranched hydrophobe; A1O is a polyoxyalkylene unit; L1 is an aliphatic linking segment or an aromatic linking segment each having at least two hydroxyl reactive linking groups; and R1 is an aliphatic end unit or aromatic end unit having 6 to 32 carbon atoms; n ranges from 3 to 6; and (b) a polymer having the formula R2-(A2O)-L2-(A2O)—R2, wherein (A2O) is a polyoxyalkylene unit, L2 is a aliphatic linking segment or an aromatic linking segment, and R2 is a aliphatic unit or an aromatic unit each having 6 to 32 carbon atoms.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. ProvisionalApplication No. 62/504,625 filed May 11, 2017, which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to ICI thickener compositions which areuseful for modifying the rheological properties of paint formulations.

BACKGROUND OF THE INVENTION

Rheology modifiers are used in waterborne coatings formulations tocontrol viscosity over a wide shear rate range. They may be associative(they associate with the dispersed phase) or non-associative (theythicken the water phase). Associative thickeners may be derived fromnatural products such as hydrophobically modified cellulose ethers, orprepared from synthetic polymers such as hydrophobically modifiedethylene oxide urethane (HEUR) polymers. U.S. Pat. No. 4,155,892 (Emmonset al.) describes the preparation of linear as well as branched HEURpolymers in separate examples.

SUMMARY OF THE INVENTION

In one embodiment, the present disclosure provides for a viscosityregulating composition comprising a mixture of (a) a branched polymerhaving the formula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n), wherein M ispolybranched hydrophobe; A¹O is a polyoxyalkylene unit; L¹ is analiphatic linking segment or an aromatic linking segment each having atleast two hydroxyl reactive linking groups; and R¹ is an aliphatic endunit or aromatic end unit having 2 to 32 carbon atoms; n ranges from 3to 6; and (b) a polymer having the formula R²-(A²O)-L²-(A²O)—R², wherein(A²O) is a polyoxyalkylene unit, L² is a aliphatic linking segment or anaromatic linking segment, and R² is a aliphatic unit or an aromatic uniteach having 2 to 32 carbon atoms.

In some embodiments, the viscosity regulating composition furthercomprises a polybranched polymer selected from (i)[R³-(A³O)-L³-(A³O)]_((n-1))-M-[(A³O)-L³-(A³O)]-M-[(A³O)-L³-(A³O)—R³]_((n-1));(ii) {[R⁴-(A⁴O)-L⁴-(A⁴O)]_((n-1))-M-[(A⁴O)-L⁴-(A⁴O)]}{-M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))-[(A⁴O)-L⁴-(A⁴O)]}_(m)-{M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-1))};(iii) and combinations thereof. In such embodiments, L³ and L⁴ are eachan aliphatic linking segment or an aromatic linking segment each havingat least two hydroxyl reactive linking groups; and R³ and R⁴ are each analiphatic end unit or aromatic end unit having 2 to 32 carbon atoms; nranges from 3 to 6.

In some embodiments, the viscosity regulating composition furthercomprises a second polymer having the formula[M]-[(A¹O)-{L¹-(A¹O)}_(m)—R¹]_(n) wherein m ranges from 2 to 4.

In some embodiments of the foregoing viscosity regulating compositions,the polyhydric alcohol is independently selected from the groupconsisting of: trimethanolpropane, pentaerythritol, dipentaerythritol,erythritol, xylitol, sorbitol, mannitol, inositol, glycopyranose andmixtures thereof.

In some embodiments of the foregoing viscosity regulating composition,(A¹O), (A²O), (A³O) and (A⁴O) each have a structure independentlyselected from:

(i) -(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-where q+x+z ranges from 50 to 250 and y ranges from 0 to 50; and (EO)and (PO) of [(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)];(ii) -(-EO—)_(q)(—PO—)_(y)(-EO—)_(z)-, where q+z ranges from 50 to 250and y ranges from 2 to 50; and (EO) and (PO) are block copolymers;(iii) -(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-, where x+z rangesfrom 50 to 250 and q+y ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) is a block polymer. PO of(—PO—)_(q) can be directly linked to either R and/or M;(iv) -(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where q+x rangesfrom 50 to 250 and y+z ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(z) is a block polymer. PO of(—PO—)_(z) is linked to L; or (v)-(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where x ranges from 50 to250 and q+y+z ranges from 4 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) and (—PO—)_(z) are blockpolymers.

In yet another embodiment, the present disclosure provides for anaqueous thickener composition including the various embodiments ofviscosity regulating composition described herein and a viscositysuppressing additive selected from an organic co-solvent, a surfactant,or combinations thereof, and water. In some embodiments, the aqueousthickener composition includes 5 wt. % to 50 wt. % of the compositionand water.

In still yet another embodiment, the present disclosure provides for anaqueous thickener composition including the various embodiments ofviscosity regulating composition described herein and water. In such anembodiment, the aqueous thickener composition does not contain aviscosity suppressant such as an organic solvent, includingbutoxyethanol, diethylene glycol monobutyl ether, triethylene glycolmonobutyl ether, propylene glycol, and other water miscible organicsolvents, an inorganic salt, such as sodium chloride or a nonionic oranionic surfactant

In still yet another embodiment, the present disclosure provides for amethod to improve ICI viscosity of an aqueous composition. An effectiveamount of a viscosity regulating composition is provided to an aqueouscomposition, wherein the ICI viscosity of the aqueous composition rangesfrom 0.5 to 5.0 Poise.

DETAILED DESCRIPTION OF THE EMBODIMENTS

As used herein, “aliphatic” refers to saturated or partially unsaturatedlinear-, branched-, or cycloaliphatic, or combinations thereof.

As used herein, “EO” refers to ethylene oxide.

As used herein “PO” refers to propylene oxide.

In one embodiment, the present disclosure provides for a viscosityregulating composition comprising a mixture of (a) a branched polymerhaving the formula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n), wherein M ispolybranched hydrophobe; A¹O is a polyoxyalkylene unit; L¹ is analiphatic linking segment or an aromatic linking segment each having atleast two hydroxyl reactive linking groups; and R¹ is an aliphatic endunit or aromatic end unit having 2 to 32 carbon atoms; n ranges from 3to 6; and (b) a polymer having the formula R²-(A²O)-L²-(A²O)—R², wherein(A²O) is a polyoxyalkylene unit, L² is a aliphatic linking segment or anaromatic linking segment, and R² is a aliphatic unit or an aromatic uniteach having 2 to 32 carbon atoms. In such embodiments, the branchedpolymer having the formula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n) has a molecularweight ranging from 13,000 g/mole to 170,000 g/mole and the polymerhaving the formula R²-(A²O)-L²-(A²O)—R² has a molecular weight rangingfrom 4,000 g/mole to 30,000 g/mole.

In some embodiments, the viscosity regulating composition furthercomprises a poly branched polymer selected from (i)[R³-(A³O)-L³-(A³O)]_((n-1))-M-[(A³O)-L³-(A³O)]-M-[(A³O)-L³-(A³O)—R³]_((n-1));(ii) {[R⁴-(A⁴O)-L⁴-(A⁴O)]_((n-1))-M-[(A⁴O)-L⁴-(A⁴O)]}{-M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))-[(A⁴O)-L⁴-(A⁴O)]}_(m)-{M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-1))};(iii) and combinations thereof. In such embodiments, L³ and L⁴ are eachan aliphatic linking segment or an aromatic linking segment each havingat least two hydroxyl reactive linking groups; and R³ and R⁴ are each analiphatic end unit or aromatic end unit having 2 to 32 carbon atoms; nranges from 3 to 6.

In some of the foregoing embodiments, the viscosity regulatingcompositing further includes a polymer having a molecular weight higherthan {[R⁴-(A⁴O)-L⁴-(A⁴O)]_((n-1))-M-[(A⁴O)-L⁴-(A⁴O)]}{-M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))-[(A⁴O)-L⁴-(A⁴O)]}_(m)-{M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))}with end groups of [R⁴-(A⁴O)-L⁴-(A⁴O)-M-], internal segments of{-M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))-[(A⁴O)-L⁴-(A⁴O)]} and/or an internalsegment of {M-[(A⁵O)-L⁵-(A⁵O)-M-]_((n-1))}. A skilled person willunderstand that gel permeation chromatography can be used to determinethe relative molecular weights of such polymers.

In some embodiments, the viscosity regulating composition furthercomprises a second polymer having the formula[M]-[(A¹O)-{L¹-(A¹O)}_(m)—R¹]_(n) wherein m ranges from 2 to 4.

In some embodiments, the amount of branched polymer ranges from: 1 wt. %to 20 wt. %; 1 wt. % to 40 wt. %; and 1 wt. % to 90 wt. % each based onthe total weight of the viscosity regulating composition.

In some embodiments, M is a polybranched hydrophobe derived from apolyhydric alcohol having 3 to 6 reactive hydroxyl groups. In some suchembodiments of the viscosity regulating composition, M is derived from apolyhydric alcohol independently selected from the group consisting of:trimethanolpropane, pentaerythritol, erythritol, dipentaerythritol,xylitol, sorbitol, mannitol, inositol, glycopyranose and mixturesthereof. In another embodiment M is derived from alkoxylated aminesindependently selected from the group consisting of: triethanolamine,N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine,N,N,N′,N″,N″-pentakis(2-hydroxyethyl)diethylenetriamine, N,N,N′,N″,N′″,N′″-hexakis(2-hydroxyethyl)triethylenetetramine, triisopropanolamine,N,N,N′,N′-tetrakis(2-hydroxyisopropyl)ethylenediamine,N,N,N′,N″,N″-pentakis(2-hydroxyisopropyl)diethylenetriamine,N,N,N′,N″,N′″, N′″-hexakis(2-hydroxyisopropyl)triethylenetetramine.

In some embodiments of the foregoing viscosity regulating composition,(A¹O), (A²O), (A³O), (A⁴O) and (A⁵O) each have a structure independentlyselected from:

(i) -(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-where q+x+z ranges from 50 to 250 and y ranges from 0 to 50; and (EO)and (PO) of [(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)];(ii) -(-EO—)_(q)(—PO—)_(y)(-EO—)_(z)-, where q+z ranges from 50 to 250and y ranges from 2 to 50; and (EO) and (PO) are block copolymers;(iii) -(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-, where x+z rangesfrom 50 to 250 and q+y ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) is a block polymer. PO of(—PO—)_(q) can be directly linked to either R and/or M;(iv) -(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where q+x rangesfrom 50 to 250 and y+z ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(z) is a block polymer. PO of(—PO—)_(z) is linked to L; or(v) -(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where x ranges from50 to 250 and q+y+z ranges from 4 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) and (—PO—)_(z) are blockpolymers.

In some embodiments of the foregoing viscosity regulating compositionL¹, L², L³, L⁴ and L⁵ are each independently an aliphatic linkingsegment or an aromatic linking segment having at least two linkinggroups. In some embodiments of the foregoing viscosity regulatingcomposition L² is an aliphatic linking segment or an aromatic linkingsegment having at least two linking groups. In some embodiments, L¹, L²,L³, L⁴ and L⁵ may be the same aliphatic linking segment or aromaticlinking segment. In some embodiments, L¹, L², L³, L⁴ and L⁵ may bedifferent aliphatic linking segment or aromatic linking segment.

In some embodiments of the foregoing viscosity regulating compositions,L¹, L², L³, L⁴ and L⁵ are each independently aliphatic linking segmentor an aromatic linking segment each having at least two linking groupseach independently selected from: urethane linking group (O—C(═O)—NH),urea linking group (N(R)—C(═O)—NH), ether linking group (—O—), esterlinking group (—C(═O)O—), amine linking group (—NH—), an aminoplastsegment, a linking group which is the residue from reaction of anepihalohydrin and a hydroxyl group. In such embodiments, the aliphaticlinking segment or an aromatic linking segment, L¹, L², L³, L⁴ and L⁵may have the same linking groups. In other such embodiments, thealiphatic linking segment or an aromatic linking segment L¹, L², L³, L⁴and L⁵ may have different linking groups.

In some embodiments, the aliphatic linking segment or aromatic linkingsegment, L¹, L², L³, L⁴ and L⁵, may have an urethane linking groupderived from a diisocyanate independently selected from the groupconsisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylenediisocyanate, 4,4′-methylenebis(isocyanatocyclohexane),1,4-cyclohexylene diisocyanate, isophorone diisocyanate, m- andp-phenylene diisocyanate, 2,6- and 2,4-toluene diisocyanate, xylenediisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4,4′-biphenylenediisocyanate, 4,4′-methylene diphenyldiisocyanate, 1,5-naphthylenediisocyanate, 1,5-tetrahydronaphthylene diisocyanate and mixturesthereof. In a certain embodiment, L¹ and/or L² are urethane linkinggroups derived from a diisocyanate independently selected from the groupconsisting 1,4 tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate or isophorone diisocyanate.

In other embodiments, the aliphatic linking segment or aromatic linkingsegment, L¹, L², L³, L⁴ and L⁵, may have an ester linking group derivedfrom a diacid independently selected from the group consisting of:propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioicacid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioicacid and mixtures thereof. In still other such embodiments, thealiphatic linking segment or aromatic linking segment, L¹ and/or L², mayhave an ester linking group derived from a diester independentlyselected from the group consisting of dimethyl succinate, dimethyladipate, dimethyl glutarate, dimethyl pimelate, dimethyl suberate,dimethyl azelate, dimethyl sebacate, diethyl succinate, diethyl adipate,diethyl glutarate, diethyl pimelate, diethyl suberate, diethyl azelate,diethyl sebacate and combinations thereof.

In yet still other such embodiments, the aliphatic linking segment oraromatic linking segment, L¹, L², L³, L⁴ and L⁵, may have an etherlinking group derived independently selected from the group consistingof: 1,3-butadiene diepoxide, 1,2,7,8-diepoxyoctane,1,2,5,6-diepoxycyclooctane, limonene diepoxide, bis(polyoxyethylenebis[glycidyl ether], bisphenol A diglycidyl ether, diglycidyl ether,ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether andcombinations thereof

In yet other such embodiments, the aliphatic linking segment or aromaticlinking segment, L¹, L², L³, L⁴ and L⁵, may have an ether linking groupderived from a dihalo compound independently selected from the groupconsisting of dihalomethane, dihaloethane, dihalopropane, dihalobutane,dihalopentane, dihalohexane, dihaloheptane, dihalooctane, dihalononane,dihalodecane, dihalododecane, and combinations thereof.

In some embodiments of the foregoing viscosity regulating compositions,R¹, R², R³ and/or R⁴ are each independently selected from the groupconsisting of a linear alkyl group, a branched alkyl group, a cyclicalkyl group, a linear alkylaryl group, a branched alkylaryl group andcombinations thereof. In some such embodiments, the alkyl group, of thelinear alkyl group, a branched alkyl group, a cyclic alkyl group, has 2to 16, 6 to 14 or 6 to 12 carbon atoms.

In some such embodiments, R¹, R², R³ and/or R⁴ are each independentlyselected from butyl, hexyl, ethylhexyl, octyl, decyl, dodecyl,tetradecyl, hexadecyl, 2-butyloctyl and 2-hexyldecyl, tristyryl phenol,distyryl phenol, styryl phenol and combinations thereof.

In one embodiment of the foregoing viscosity regulating compositions,the linear alkyl group or branched alkyl group, of R¹, R², R³ and/or R⁴,are respectively derived from a linear aliphatic alcohol or branchedaliphatic alcohol wherein the alkyl group has 4 to 16, 6 to 14 or 6 to12 carbon atoms. In one embodiment, the linear alkyl alcohol or branchedalkyl alcohol independently includes 2-ethylhexanol, 1-octanol,1-nonanol, 1-decanol, 1-dodecanol, or 1-tetradecanol. In anotherembodiment the aliphatic alcohol is derived from di-n-octylaminoethanol,1-(dibutylamino)-2-butanol, di-2-ethylhexylaminoethanol,di-hexylaminoethanol, 2-(dioctylamino)-ethanol, 2-(dibutylamino)ethanol, 2-(diheptylamino) ethanol, 2-(dihexylamino) ethanol,2-(dicocoamino) ethanol, 6-dipropylamino-1-hexanol,1-(bis(3-(dimethylamino)propyl)amino)-2-propanol, and2-(diethylhexylamino)-ethanol. In some embodiments, the alkyl group isderived from 1-decanol, 2-(n-butyl)-1-octanol, 2-ethylhexanol,1-nonanol, 1-dodecanol and mixtures thereof.

In one embodiment of the foregoing viscosity regulating compositions,the linear alkyl group or branched alkyl group, of R¹, R², R³ and/or R⁴,are derived from an amine selected from, diethylamine, diallylamine,dipropylamine, diisopropylamine, dibutylamine, dipentylamine,dihexylamine, dioctylamine, di-(2-ethylhexyl)amine, dicyclohexylamine,dibenzylamine, morpholine, piperidine, pyrrolidine, N-methylpiperazineand the product of these amines with epoxides.

In one embodiment of the foregoing viscosity regulating compositions, alinear alkylaryl group or a branched alkylaryl group, of R¹, R², R³and/or R⁴, are derived from an aromatic alcohol wherein the aryl grouphas 6 to 32 carbon atoms, 6 to 22 carbon atoms or 6 to 14 carbon atoms.In one such embodiment, the linear alkylaryl group or branched alkylarylgroup are independently derived from tristyryl phenol, distyryl phenol,styryl phenol and mixtures thereof.

In one certain embodiment of the viscosity regulating composition, thecomposition comprises a mixture of (a) a branched polymer having theformula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n), wherein M is derived fromtrimethylolpropane, A¹O is a polyoxyalkylene unit, L¹ is derived from1,4 tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R¹ is derived from decanol, dodecanol ortetradecanol; and (b) a polymer having the formula R²-(A²O)-L²-(A²O)—R²,wherein (A²O) is a polyoxyalkylene unit, L² is derived from 1,4tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R² is derived from decanol, dodecanol ortetradecanol. In one such embodiment, the viscosity regulatingcomposition may further include one or more polybranched polymerselected from (i)[R³-(A³O)-L³-(A³O)]₂-M-[(A³)-L³-(A³O)]-M-[(A³O)-L³-(A³O)—R³]₂; (ii){[R³(A³O)-L³(A³O)]₂-M-[(A³O)-L³-(A³O)]}-{M-[(A³O)-L³-(A³O)—R³]—[(A³O)-L³-(A³O)]}₍₂₋₄₎-M-[(A³O)-L³-(A³O)—R³]₂;and (iii) combinations thereof; wherein L³ is independently derived from1,4 tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R³ is independently derived from decanol,dodecanol or tetradecanol. For the foregoing embodiments, the branchedpolymer having the formula [M]-[(A¹O)-L¹-(A¹O)—R]_(n) has a molecularweight ranging from 13,000 g/mole to 90,000 g/mole and the polymerhaving the formula R²-(A²O)-L²-(A²O)—R² has a molecular weight rangingfrom 4,000 g/mole to 30,000 g/mole. For the foregoing embodiments,(A¹O), (A²O) and (A³O) each have a structure according to formula (I):

-(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-, where q+x+z ranges from50 to 250 and y ranges from 0 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)].

In one certain embodiment of the viscosity regulating composition, thecomposition comprises a mixture of (a) a branched polymer having theformula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n), wherein M is derived frompentaerythritol, A¹O is a polyoxyalkylene unit, L¹ is derived from 1,4tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R¹ is derived from decanol, dodecanol ortetradecanol; and (b) a polymer having the formula R²-(A²O)-L²-(A²O)—R²,wherein (A²O) is a polyoxyalkylene unit, L² is derived from 1,4tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R² is derived from decanol, dodecanol ortetradecanol. In one such embodiment, the viscosity regulatingcomposition may further include one or more polybranched polymerselected from (i)[R³-(A³O)-L³-(A³O)]₃-M-[(A³O)-L³-(A³O)]-M-[(A³O)-L³-(A³O)—R³]₃; (ii){[R³(A³O)-L³(A³O)]₃-M-[(A³O)-L³-(A³O)]}-{M-[(A³O)-L³-(A³O)—R³]₂-[(A³O)-L³-(A³O)]}₍₂₋₄₎-M-[(A³O)-L³-(A³O)—R³]₃;and (iii) and combinations thereof, wherein L³ is independently derivedfrom 1,4 tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate orisophorone diisocyanate, and R³ is independently derived from decanol,dodecanol or tetradecanol. In such embodiments, the branched polymerhaving the formula [M]-[(A¹O)-L¹-(A¹O)—R¹]_(n) has a molecular weightranging from 17,000 g/mole to 120,000 g/mole and the polymer having theformula R²-(A²O)-L²-(A²O)—R² has a molecular weight ranging from 4,000g/mole to 30,000 g/mole. In the foregoing embodiments, (A¹O), (A²O) and(A³O) each have a structure according to formula (I):-(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-, where q+x+z ranges from50 to 250 and y ranges from 0 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)].

The present disclosure further provides for an aqueous thickeningcomposition containing the various embodiments of the viscosityregulating composition described herein and water. In some embodiments,the aqueous thickening composition may contain 5-50 wt. % of the ICIviscosity regulating composition described herein and water. In someembodiments, the aqueous thickening composition may contain 5-30 wt. %of the ICI viscosity regulating composition described herein and water.In some embodiments, the aqueous thickening composition may contain15-30 wt. % of the ICI viscosity regulating composition described hereinand water. In such embodiments of the aqueous thickening composition,the aqueous thickening composition does not contain a viscositysuppressant when the viscosity, of the aqueous thickening composition isless than 10000 cP. Such viscosity suppressants include organicsolvents, such as butoxyethanol, diethylene glycol monobutyl ether,triethylene glycol monobutyl ether, propylene glycol, and other watermiscible organic solvents, an inorganic salt, such as sodium chloride ora nonionic or anionic surfactant. In some such embodiments, the aqueousthickening composition further contains a biocide, an anti-oxidant andcombinations thereof. In the foregoing embodiments, the aqueousthickening composition may have a viscosity ranging from: 100 to 2500 cPor 100 to 5000 cP or 100 to 10000 cP.

The present disclosure further provides for an aqueous thickeningcomposition containing the various embodiments of the viscosityregulating composition described herein, a viscosity suppressant andwater. In some embodiments, the aqueous thickening composition maycontain 5-50 wt. % of the ICI viscosity regulating composition describedherein, a viscosity suppressant and water. In some embodiments, theaqueous thickening composition may contain 5-30 wt. % of the ICIviscosity regulating composition described herein, a viscositysuppressant and water. In some embodiments, the aqueous thickeningcomposition may contain 15-30 wt. % of the ICI viscosity regulatingcomposition described herein, a viscosity suppressant and water. In suchembodiments, the viscosity suppressant includes organic solvents, suchas butoxyethanol, diethylene glycol monobutyl ether, triethylene glycolmonobutyl ether, propylene glycol, and other water miscible organicsolvents, an inorganic salt, such as sodium chloride or a nonionic oranionic surfactant. In some such embodiments, the aqueous thickeningcomposition further contains a biocide, an anti-oxidant and combinationsthereof. In the foregoing embodiments, the aqueous thickeningcomposition may have a viscosity of up to: 2500 cP; 5000 cP; 10,000 cP;15,000 cP; 20,000 cP; or 25,000 cP. In one such embodiment, the aqueousthickening composition may have a viscosity ranging from: 100 to 2500cP; 100 to 5000 cP; 100 to 10000 cP; 100 to 15,000 cP; 100 to 20,000 cP;or 100 to 25,000 cP. In one embodiment, the aqueous thickening may havea viscosity ranging from: 100 to 2500 cP or 100 to 5000 cP.

The Brookfield viscosities of such aqueous thickening compositions aremeasured at 25° C. and 10 RPM using a Brookfield RV or RVT. Typically a#1 spindle is used for materials having a Brookfield viscosity of400-600 cP (40-60 dial reading), a #2 spindle is used for materialshaving a Brookfield viscosity of 1600-2400 cP and a #3 spindle is usedfor materials having a Brookfield viscosity of 4000-6000 cP. Thefollowing table may also be used to determine the appropriate spindle touse when measuring Brookfield viscosity at 25° C. and 10 RPM:

Viscosity (cP) Spindle Factor Mid-dial Max 1 10 500 1000 2 40 2000 40003 100 5000 10000 4 200 10000 20000 5 400 20000 40000 6 1000 50000 1000007 4000 200000 400000

In another embodiment, the present invention provides for a method toimprove ICI viscosity of an aqueous composition comprising: providing aneffective amount of a viscosity regulating composition according to thevarious embodiments described herein to an aqueous composition, whereinthe ICI viscosity of the aqueous composition ranges from 0.5 to 5.0Poise.

Methods of Manufacture

The present disclosure provides for various methods of manufacturing thevarious embodiments of the viscosity regulating composition describedherein. For each of the embodiments of methods of manufacturing,described below, the skilled person should look to the description of M,L, R and AO as described above herein for the various embodiments of theviscosity regulating composition.

In one embodiment, the present disclosure provides for a method ofmanufacturing a viscosity regulating composition comprising thefollowing steps. A solvent-free melt is formed of (i) an alkoxylatedpolyhydroxyl segment, having the formula [M]-(AO)_(n) having 3 to 6reactive hydroxyl linking groups, n ranges from 3 to 6, a molecularweight ranging from 10,000 g/mole to 50,000 g/mole, and (ii) analkoxylated aliphatic end segment or alkoxylated aromatic end segment,having the formula (AO)—R and a reactive hydroxyl linking group and amolecular weight ranging from 2,000 g/mole to 10,000 g/mole. Thesolvent-free melt is contacted with aliphatic linking segments oraromatic linking segments, L, each having at least two hydroxyl reactivelinking groups under conditions sufficient to form a compositioncomprising a mixture of a branched polymer having the formula[M]-[(AO)-L-(AO)—R]_(n) and a polymer having the formulaR-(AO)-L-(AO)—R, wherein the mole ratio of the alkoxylated polyhydroxylsegment to the alkoxylated aliphatic end segment or alkoxylated aromaticend segment ranges from 1:3 to 1:30; 1:3 to 1:14; 1:9 to 1:22. Incertain embodiments, the composition further comprises a poly branchedpolymer selected from (i)[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]-M-[(AO)-L-(AO)—R]_((n-1)); (ii){[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]}{-M-[(AO)-L-(AO)—R]_((n-2))-[(AO)-L-(AO)]}_(m)-{M-[(AO)-L-(AO)—R]_((n-1))};(iii) and combinations thereof.

In another embodiment, the present disclosure provides for a method ofmanufacturing a viscosity regulating composition comprising thefollowing steps. A solvent-free melt is formed of (i) an alkoxylatedpolyhydroxyl segment, having the formula [M]-(AO)_(n) having 3 to 6reactive hydroxyl linking groups, n ranges from 3 to 6, a molecularweight ranging from 1,000 g/mole to 10,000 g/mole, and (ii) analkoxylated aliphatic end segment or alkoxylated aromatic end segment,having the formula (AO)—R, a reactive hydroxyl linking group and amolecular weight ranging from 500 g/mole to 2,000 g/mole. Thesolvent-free melt is contacted with ethylene oxide, propylene oxide orcombination thereof under conditions sufficient to form a mixture of analkoxylated polyhydroxyl segment having a molecular weight ranging from10,000 g/mole to 50,000 g/mole and an alkoxylated aliphatic end segmentor alkoxylated aromatic end segment having a molecular weight rangingfrom 2,000 g/mole to 10,000 g/mole. The solvent-free melt is thencontacted with aliphatic linking segments or aromatic linking segments,L, each having at least two hydroxyl reactive linking groups underconditions sufficient to form a composition comprising a mixture of abranched polymer having the formula [M]-[(AO)-L-(AO)—R]_(n) and apolymer having the formula R-(AO)-L-(AO)—R, wherein the mole ratio ofthe alkoxylated polyhydroxyl segment to the alkoxylated aliphatic endsegment or alkoxylated aromatic end segment ranges from 1:3 to 1:30; 1:3to 1:14; 1:9 to 1:22. In certain embodiments, the composition furthercomprises a poly branched polymer selected from (i)[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]-M-[(AO)-L-(AO)—R]_((n-1)); (ii){[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]}{-M-[(AO)-L-(AO)—R]_((n-2))-[(AO)-L-(AO)]}_(m)-{M-[(AO)-L-(AO)—R]_((n-1))};(iii) and combinations thereof.

In another embodiment, the present disclosure provides for a method ofmanufacturing viscosity regulating composition comprising the followingsteps. At least two moles of an alkoxylated aliphatic end segment oralkoxylated aromatic end segment, having the formula (AO)—R and areactive hydroxyl linking group and a molecular weight ranging from2,000 g/mole to 10,000 g/mole, are reacted with aliphatic linkingsegments or aromatic linking segments, L, having at least two hydroxylreactive linking groups under conditions sufficient to form acomposition having a formula of R-(AO)-L-(AO)—R. The composition havinga formula of R-(AO)-L-(AO)—R is added to a solvent free melt of (i) analkoxylated polyhydroxyl segment, having the formula [M]-(AO)_(n) having3 to 6 reactive hydroxyl linking groups, n ranges from 3 to 6, amolecular weight ranging from 10,000 g/mole to 50,000 g/mole, and (ii)an alkoxylated aliphatic end segment or alkoxylated aromatic endsegment, having the formula (AO)—R and a reactive hydroxyl linking groupand a molecular weight ranging from 2,000 g/mole to 10,000 g/mole. Thesolvent-free melt is contacted with aliphatic linking segments oraromatic linking segments, L, each having at least two hydroxyl reactivelinking groups under conditions sufficient to form a composition havingthe formula branched polymer having the formula [M]-[(AO)-L-(AO)—R]_(n),wherein the mole ratio of the alkoxylated polyhydroxyl segment to thealkoxylated aliphatic end segment or alkoxylated aromatic end segmentranges from 1:3 to 1:30; 1:3 to 1:14; 1:9 to 1:22. In certainembodiments, the composition further comprises a poly branched polymerselected from (i)[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]-M-[(AO)-L-(AO)—R]_((n-1)); (ii){[R-(AO)-L-(AO)]_((n-1))-M-[(AO)-L-(AO)]}{-M-[(AO)-L-(AO)—R]_((n-2))-[(AO)-L-(AO)]}_(m)-{M-[(AO)-L-(AO)—R]_((n-1))};(iii) and combinations thereof.

Paint Formulations

A variety of paint formulations may be formulated using the viscosityregulating composition described herein and/or the aqueous thickeningcompositions, as described herein. In one embodiment, a paintformulation includes: 10-50 wt. % solids of a resin system; 0.0-2.0 wt.% actives of an associative co-thickener; 0.1-3.0 wt. % actives of theICI viscosity regulating composition according to the variousembodiments discussed herein; and optionally 1-12 wt. % of a colorantcomposition.

In one embodiment, the ICI viscosity of a paint formulation ranges from0.5 to 5.0 Poise. In another embodiment, the ICI viscosity of a paintformulation ranges from 0.5 to 4.0 Poise. In yet another embodiment, theICI viscosity of a paint formulation ranges from 0.5 to 3.0 Poise. Instill yet another embodiment, the Stormer viscosity of a paintformulation is at least 60 KU. In another such embodiment, the Stormerviscosity of a paint formulation ranges from 60 KU to 130 KU.

A paint formulation of some embodiments of the present invention mayinclude one or more resin film forming binders. A binder, or resin, isthe actual film forming component of paint. It is an essential componentof a base paint; and other components listed herein are includedoptionally, depending on the desired properties of the cured film.Binders can be categorized according to drying, or curing mechanism. Thefour most common are simple solvent evaporation, oxidative crosslinking,catalyzed polymerization, and coalescence.

In some embodiments, the resin binder is a water dispersible resin, suchas a water dispersible alkyd or water dispersible polyurethane. In someembodiments, the resin binder is a water soluble resin. In certainembodiments, the resin binder is an emulsion resin, such as is typicallyused to manufacture latex paints. In certain embodiments, the resinincludes a hydrophobic resin. Representative hydrophobic emulsion resinsmay include (meth)acrylic resin, a styrene acrylic resin, a styreneresin or other ethylenically unsaturated monomers. Representativeexamples of hydrophilic emulsion resins may include a vinyl acrylicresin or a vinyl acetate ethylene resin. In certain embodiments, theresin may have a substantially spherical shape and a large particle sizeor low surface area. In one embodiment, the particle size may be greaterthan about 200 nm. In a further embodiment, the particle size rangesfrom about 220 nm to about 650 nm. In certain embodiments, the resin mayhave a substantially spherical shape and small particle size or highsurface area. In one embodiment, the particle size may be less thanabout 200 nm. In a further embodiment, the particle size ranges fromabout 40 nm to about 180 nm. In certain embodiments, the resin may havea multilobe shape. Representative resins may include Optive 130 (BASF,acrylic, 160 nm), UCAR 300 (Dow, vinyl acrylic, 260 nm), UCAR 625 (Dow,acrylic, 340 nm), Rhoplex ML-200 (Rohm & Haas, acrylic, 590 nmmultilobe), and Neocryl XK-90 (DSM Neoresins, acrylic, 90 nm). Incertain embodiments, combinations of resins are used to prepare the basepaint.

The paint formulation may also include at least one associativeco-thickener. Associative co-thickeners are water soluble, waterdispersible, or water swellable polymers that have chemically attachedhydrophobic groups. In certain embodiments, a paint formulation includesa condensation polymer associative co-thickener including but notlimited to polyether polyurethanes, polyether polyols, polyetherpolyacetals, polyether aminoplasts and the like. In some embodiments, apaint formulation includes about 0.05 wt % to about 5 wt % as activepolymer of a condensation polymer associative co-thickener, about 0.1 wt% to about 3 wt % as active polymer of a condensation polymerassociative co-thickener, or about 0.2 wt % to about 1 wt % as activepolymer of a condensation polymer associative co-thickener.

In some embodiments, the associative co-thickener includes polyurethanethickener; a hydrophobically modified cellulose; a hydrophobicallymodified alkali soluble thickener; an alkali soluble thickener; acellulose thickener; a polyacetalpolyether; polyetherpolyol thickener;smectite clays and mixtures thereof.

In other embodiments, the associative co-thickeners include nonionichydrophobically modified materials including nonionichydrophobically-modified ethylene oxide urethane copolymers, nonionichydrophobically-modified ethylene oxide ether copolymers, nonionichydrophobically-modified ethylene oxide glycouril copolymers,hydrophobically-modified alkali soluble emulsions,hydrophobically-modified poly(meth)acrylic acids,hydrophobically-modified hydroxyethyl cellulose, andhydrophobically-modified poly(acrylamide), and mixtures thereof. Thenumber average molecular weights of the associative co-thickeners mayrange from about 10,000 to about 500,000 g/mole or more, depending onthe chemical type of associative thickener. In some embodiments, thenumber average molecular weight of the associate do-thickeners may rangefrom about 10,000 to about 50,000 g/mole. In some embodiments, thenumber average molecular weight of the associate co-thickeners may rangefrom about 100,000 to about 300,000 g/mole. In some embodiments, thenumber average molecular weight of the associate co-thickeners may rangefrom about 400,000 to about 500,000 g/mole or more.

In another embodiment, the associative co-thickener may include an KUassociative thickener which is used to increase the low to mid shearviscosity of a composition.

A colorant containing paint formulation of the present invention mayalso include any suitable colorant. In some embodiments, a predispersedcolorant may be added to a paint formulation. It is to be understoodthat this invention is equally effective with single colorants ormixtures of colorants.

Within the context of this invention, a colorant or colorant compoundmay include one or more colored pigment(s) which have been dispersed inan aqueous or water-miscible medium external to the paint in which it isintended to be used by use of mechanical energy, i.e., grinding orshearing by means of dispersing equipment such as, for example, a ballmill and a sand mill and then dispersed into a base paint. For thepurposes of this disclosure, colorant does not include pigments in a dryundispersed state. The dispersion process is typically achieved by theuse of auxiliary compounds such as, for example, surfactants, wettingagents, water-miscible solvents, and dispersants, in addition tomechanical energy. The aqueous or water-miscible medium may also includeglycols such as ethylene glycol and propylene glycol, and alcohols suchas isopropanol. Dispersants may include polyethylene oxide polymers,polyethylene oxide glycols and others. The aqueous or water-misciblemedium may also include extenders such as talc and calcium carbonate;humectants; thickeners; defoamer; and biocides. Such colorants arefrequently added to a base paint or tint base at the point-of-sale toproduce custom colors.

Pigments which are commonly used to prepare colorants include one ormore inorganic or organic pigments, or metal effect agents, orcombinations thereof. Examples of suitable pigments include titaniumdioxide white, carbon black, lamp black, black iron oxide, red ironoxide, yellow iron oxide, brown iron oxide (a blend of red and yellowoxide with black), phthalocyanine green, phthalocyanine blue, organicred pigment (such as naphthol red, quinacridone red and toluidine red),quinacridone magenta, quinacridone violet, DNA orange, and organicyellow pigment (such as Hansa yellow) and combinations thereof.

The colorants are usually sold in concentrated form (typically 25% to75% solids by weight) so that modest amounts can be used in a waterbornecoating composition to provide a desired range of color intensitieswhile not compromising the properties of the waterborne coatingcomposition unduly. Typical amounts of colorants which are used inarchitectural coatings are from 2 to 4 fluid ounces of colorant pergallon of base paint for light tint bases and pastels, from 4 to 8 fluidounces of colorant per gallon of base paint for medium tint bases, andfrom 6 to 16 fluid ounces of colorant per gallon of base paint for deeptone tint bases. Of course, different colorants and mixtures thereof arefrequently used to provide wide latitude in color selection. Suchcolorants are frequently added to a base paint at the point-of-purchaseof the colored paint, such as a paint store, followed by admixing thecolorant and the waterborne coating composition by various means such asshaking the can of paint.

A paint system of some embodiments of the present invention may includeadditional components as suitable to achieve the desire effect,including but not limited to wetting agents, fillers; pigments, such astitanium dioxide, mica, calcium carbonate, silica, zinc oxide, milledglass, aluminum trihydrate, talc, antimony trioxide, fly ash, and clay;polymer encapsulated pigments, such as polymer-encapsulated or partiallyencapsulated pigment particles such as titanium dioxide, zinc oxide, orlithopone particles; polymers or polymer emulsions adsorbing or bondingto the surface of pigments such as titanium dioxide; hollow pigments,including pigments having one or more voids; dispersants, such asaminoalcohols and polycarboxylates; surfactants; defoamers;preservatives, such as biocides, mildewcides, fungicides, algaecides,and combinations thereof; flow agents; leveling agents; and additionalneutralizing agents, such as hydroxides, amines, ammonia, andcarbonates.

Paint formulations may be characterized by a variety of propertiesincluding Stormer (KU) viscosity, ICI viscosity, sag and leveling.

Stormer viscosity relates to the in-can appearance and is typicallymeasured in Krebs units (KU) using a Stormer viscometer. Mid-shear orStormer viscosity was measured by the test method described in ASTMD562-01 “Standard Test Method Consistency of Paints Measuring Krebs Unit(KU) Viscosity Using a Stormer-Type Viscometer.”

ICI viscosity represents the viscosity of the paint during typical brushand roller application conditions. It is typically measured at 10,000sec¹ by the test method described in ASTM D4287-00 “Standard Test Methodfor High-Shear Viscosity Using a Cone/Plate Viscometer.”

The sag and leveling properties of a film, on a substrate, formed byapplication of a paint formulation, containing the mid-shear regulatingcomposition, were also measured. Sag values were measured following thetest method described in ASTM D4400-99 (Reapproved 2007) “Standard TestMethod for Sag Resistance of Paints Using a Multinotch Applicator.” Theleveling values were measured following the test method described inASTM D4062-99 (Reapproved 2003) “Standard Test Method for Leveling ofPaints by Draw-Down Method.”

By way of a non-limiting example, the compounds encompassed herein areused to make high-shear (e.g., ICI) viscosity regulating compositions.

For the purposes of this disclosure, the term “about” means plus orminus 10%.

EXAMPLES

The following examples further describe and demonstrate illustrativeembodiments within the scope of the present invention. The examples aregiven solely for illustration and are not to be construed as limitationsof this invention as many variations are possible without departing fromthe spirit and scope thereof. For reactions using diisocyanatereactants, a catalyst such as an organo-tin or bismuth ester or an aminemay be added to accelerate the reaction at the desired temperature.

Example 1

A viscosity regulating composition was prepared as follows: To a 500 mlreaction kettle equipped with a nitrogen inlet, stirrer, Dean Stark trapand a condenser, 50.00 g of alkoxylated trimethylolpropane (Mn: 18160,2.75 mmol), 52.65 g of alkoxylated lauryl alcohol (Mn: 6375, 8.25 mmol),0.15 g benzoic acid (MW: 122.12, 1.23 mmol) and 300 g of toluene wereadded. The alkoxylate groups of alkoxylated trimethylolpropane andalkoxylated lauryl alcohol were a mixture of ethylene oxide andpropylene oxide. The reaction mixture was stirred at 250 rpm anddewatered at 130° C., with a N₂ purge, 0.5 ml/min, to remove 120 ml ofthe toluene/H₂O mixture. The reaction was cooled to 80° C. followed byaddition of 1.39 g of hexamethylene diisocyanate (HDI) (MW: 168.19:8.26mmol) and 3 drops of K-Kat 348. The reaction is stirred at 80° C. for1.5 hour. The mixture was cooled and poured onto a metal tray toevaporate toluene. The composition was further dried in a vacuum oven.

Example 2

Same procedure described in Example A replacing the alkoxylated laurylalcohol with 52.65 g of alkoxylated decyl alcohol (Mn: 6375, 8.25 mmol).The alkoxylate group of alkoxylated decyl alcohol was a mixture ofethylene oxide and propylene oxide.

Example 3

Same procedure described in Example A replacing the alkoxylated laurylalcohol with 52.65 g of alkoxylated tetradecyl alcohol (Mn: 6375, 8.25mmol). The alkoxylate group of alkoxylated tetradecyl alcohol was amixture of ethylene oxide and propylene oxide.

Example 4

A viscosity regulating composition was prepared as follows:

(i) To a 5000 ml reaction kettle equipped with a nitrogen inlet,stirrer, and a distillation setup, 481.4 g of alkoxylated lauryl alcohol(Mn: 1620, 0.297 mol, base value: 4.0 mgKOH/g), and 121.5 g ofalkoxylated trimethylolpropane (Mn: 4500, 0.027 mol, base value: 2.9mgKOH/g) were added. The alkoxylate groups of alkoxylatedtrimethylolpropane and alkoxylated lauryl alcohol were a mixture ofethylene oxide and propylene oxide. The reaction mixture was stirred at250 rpm and dewatered at 125° C., with a N₂ purge, 0.5 ml/min, until awater content of <250 ppm was reached. The mixture was heated to 115° C.the kettle was closed. In N₂ atmosphere, 2010.6 g ethylene oxide (MW:44.10; 45.59 mol) and 305 g propylene oxide (MW: 58.08; 5.25 mol) wereadded under pressure in 8 hours. The reaction mixture was stirred at115° C. for 3 hours.

(ii) 700 g of the reaction mixture prepared in (i), was heated to 120°C. and 1.18 g benzoic acid (MW: 122.12, 9.66 mmol) was added toneutralize the base catalyst used for the alkoxylation reaction. Thereaction was stirred at 120° C. for 30 minutes, followed by dropwiseaddition of 9.44 g of hexamethylene diisocyanate (HDI) (MW: 168.19:56.15mmol). The reaction mixture was stirred at 120° C. for 1.5 hour followedby addition of water till the required dry content was reached.

Example 5

Same procedure described in Example 4 replacing 192.8 g of alkoxylatedlauryl alcohol (Mn: 1620, 0.119 mol, base value: 4.0 mgKOH/g) with 192.8g of alkoxylated decyl alcohol (Mn: 1620, 0.119 mol, base value: 4.0mgKOH/g).

Example 6

A viscosity regulating composition was prepared as follows: To a 250 mlreaction kettle equipped with a nitrogen inlet, stirrer and a condenser,50.00 g of alkoxylated pentaerythritol (Mn: 24930, 2.01 mmol), 179.38 gof alkoxylated lauryl alcohol (Mn: 6375, 24.08 mmol), and 0.39 g benzoicacid (MW: 122.12, 2.81 mmol) were added. The reaction mixture wasstirred at 250 rpm and dewatered at 130° C., with a N₂ purge, 0.5ml/min. The reaction was heated to 120° C. followed by addition of 3.26g of hexamethylene diisocyanate (HDI) (MW: 168.19:18.05 mmol). Thereaction mixture was stirred at 120° C. for 1.5 hour followed byaddition of water till the required dry content was reached.

Table 1. Brookfield viscosity of the 20 wt. % solution of the viscosityregulating composition and Brookfield/ICI viscosities of the paint(semigloss Mowilith LDM 7717, PVC30) upon addition of 0.6 wt. % of theviscosity regulating composition.

BF viscosity/cP Paint application 20 wt % solution BF viscosity/cP inwater Spindle 64, Spindle 64, ICI viscosity/P Example 12 rpm, 23° C. 12rpm, 23° C. 750 rpm, 25° C. 1 8500 4750 3.64 2 400 450 0.91 3 >100′00021′500 1.07 4 1880 4500 2.47 5 1250 1850 1.97 6 2050 3000 2.49 Benchmark1 2130 1160 1.16 Benchmark 2 2450 2100 2.19

The present disclosure may be embodied in other specific forms withoutdeparting from the spirit or essential attributes of the invention.Accordingly, reference should be made to the appended claims, ratherthan the foregoing specification, as indicating the scope of thedisclosure. Although the foregoing description is directed to thepreferred embodiments of the disclosure, it is noted that othervariations and modification will be apparent to those skilled in theart, and may be made without departing from the spirit or scope of thedisclosure.

What is claimed:
 1. A viscosity regulating composition comprising amixture of (a) a branched polymer having the formula[M]-[(A¹O)-L¹-(A¹O)—R¹]_(n) wherein M is a polybranched hydrophobe;(A¹O) is a polyoxyalkylene unit; L¹ is an aliphatic linking segment oran aromatic linking segment; R¹ is an aliphatic unit or an aromatic uniteach having 2 to 32 carbon atoms and n ranges from 3 to 6; and (b) apolymer having the formula R²-(A²O)-L²-(A²O)—R², wherein (A²O) is apolyoxyalkylene unit, L² is an aliphatic linking segment or an aromaticlinking segment, and R² is an aliphatic unit or an aromatic unit eachhaving 2 to 32 carbon atoms.
 2. The viscosity regulating composition ofclaim 1, further comprising a polybranched polymer selected from thegroup consisting of (i)[R³-(A³O)-L³-(A³O)]_((n-1))-M-[(A³O)-L³-(A³O)]-M-[(A³O)-L³-(A³O)—R³]_((n-1));(ii) {[R⁴-(A⁴O)-L⁴-(A⁴O)]_((n-1))-M-[(A⁴O)-L⁴-(A⁴O)]}{-M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-2))-[(A⁴O)-L⁴-(A⁴O)]}_(m)-{M-[(A⁴O)-L⁴-(A⁴O)—R⁴]_((n-1))};(iii) and combinations thereof.
 3. The viscosity regulating compositionof claim 2, wherein M is derived from a polyhydric alcohol independentlyselected from the group consisting of: trimethanolpropane,pentaerythritol, erythritol, dipentaerythritol, xylitol, sorbitol,mannitol, inositol, glycopyranose and mixtures thereof.
 4. The viscosityregulating composition according to claim 3, wherein (A¹O), (A²O), (A³O)and (A⁴O) each structure independently selected from: (i)-(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)- where q+x+z ranges from 50to 250 and y ranges from 0 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)]; (ii) -(-EO—)_(q)(—PO—)_(y)(-EO—)_(z)-, whereq+z ranges from 50 to 250 and y ranges from 2 to 50; and (EO) and (PO)are block copolymers; (iii)-(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](-EO—)_(z)-, where x+z ranges from 50to 250 and q+y ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) is a block polymer. PO of(—PO—)_(q) can be directly linked to either R and/or M; (iv)-(-EO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where q+x ranges from 50to 250 and y+z ranges from 2 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(z) is a block polymer. PO of(—PO—)_(z) is linked to L; or (v)-(—PO—)_(q)[(-EO—)_(x)-(—PO—)_(y)](—PO—)_(z)-, where x ranges from 50 to250 and q+y+z ranges from 4 to 50; and (EO) and (PO) of[(-EO—)_(x)-(—PO—)_(y)] are randomly distributed throughout[(-EO—)_(x)-(—PO—)_(y)] while PO of (—PO—)_(q) and (—PO—)_(z) are blockpolymers.
 5. The viscosity regulating composition of claim 4, whereinL¹, L², L³ and L⁴ each have least two linking groups independentlyselected from: urethane linking group (O—C(═O)—NH), urea linking group(N(R)—C(═O)—NH), ether linking group (—O—), ester linking group(—C(═O)O—), amine linking group (—NH—), an aminoplast segment, a linkinggroup which is the residue from reaction of an epihalohydrin and ahydroxyl group.
 6. The viscosity regulating composition of claim 5,wherein L¹, L², L³ and L⁴ each an urethane linking group derived from adiisocyanate independently selected from the group consisting of1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene diisocyanate,4,4′-methylenebis(isocyanatocyclohexane), 1,4-cyclohexylenediisocyanate, isophorone diisocyanate, m- and p-phenylene diisocyanate,2,6- and 2,4-toluene diisocyanate, xylene diisocyanate,4-chloro-1,3-phenylene diisocyanate, 4,4′-biphenylene diisocyanate,4,4′-methylene diphenyldiisocyanate, 1,5-naphthylene diisocyanate,1,5-tetrahydronaphthylene diisocyanate and mixtures thereof.
 7. Theviscosity regulating composition of claim 6, wherein L¹, L², L³ and L⁴each have an ester linking group derived from a diacid independentlyselected from the group consisting of: propanedioic acid, butanedioicacid, pentanedioic acid, hexanedioic acid, heptanedioic acid,octanedioic acid, nonanedioic acid, decanedioic acid and mixturesthereof.
 8. The viscosity regulating composition of claim 7, wherein L¹,L², L³ and L⁴ each have an ester linking group derived from a diesterindependently selected the group consisting of dimethyl succinate,dimethyl adipate, dimethyl glutarate, dimethyl pimelate, dimethylsuberate, dimethyl azelate, dimethyl sebacate, diethyl succinate,diethyl adipate, diethyl glutarate, diethyl pimelate, diethyl suberate,diethyl azelate, diethyl sebacate and combinations thereof.
 9. Theviscosity regulating polymer composition of claim 5, wherein L¹, L², L³and L⁴ each have an ether linking group derived independently selectedfrom the group consisting of: 1,3-butadiene diepoxide,1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, limonene diepoxide,bis(polyoxyethylene bis[glycidyl ether], bisphenol A diglycidyl ether,diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycoldiglycidyl ether and combinations thereof
 10. The viscosity regulatingpolymer composition of claim 9, wherein L¹, L², L³ and L⁴ each have anether linking group derived from a dihalo compound independentlyselected from the group consisting of dihalomethane, dihaloethane,dihalopropane, dihalobutane, dihalopentane, dihalohexane, dihaloheptane,dihalooctane, dihalononane, dihalodecane, dihalododecane, andcombinations thereof.
 11. The viscosity regulating composition of claim5, wherein R¹, R², R³ and R⁴ are each independently selected from thegroup consisting of a linear alkyl group, a branched alkyl group, acyclic alkyl group, a linear alkylaryl group, a branched alkylaryl groupand combinations thereof, each having 2 to 16, 6 to 14 or 6 to 12 carbonatoms.
 12. The viscosity regulating composition of claim 11, wherein R¹,R², R³ and R⁴ are independently selected from butyl, hexyl, ethylhexyl,octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, 2-butyloctyl and2-hexyldecyl, tristyryl phenol, distyryl phenol, styryl phenol andcombinations thereof.
 13. The viscosity regulating composition of claim1, further comprising a second polymer having the formula[M]-[(A¹O)-{L-(A¹O)}_(m)—R¹]_(n) wherein m ranges from 2 to
 4. 14. Anaqueous thickener composition comprising: the viscosity regulatingcomposition according to claim 1 and water.
 15. The aqueous thickenercomposition according to claim 14, having 5 wt. % to 50 wt. % of theviscosity regulating composition.
 16. The aqueous thickener compositionaccording to claim 15, further comprising a viscosity suppressantindependently selected from the group consisting of organic solvents,butoxyethanol, diethylene glycol monobutyl ether, triethylene glycolmonobutyl ether, propylene glycol, and other water miscible organicsolvents, an inorganic salt, sodium chloride or a nonionic or anionicsurfactant.
 17. The aqueous thickener composition according to claim 15,having a viscosity ranging from 100 to 10000 cP in the absence of aviscosity suppressant independently selected from the group consistingof organic solvents, butoxyethanol, diethylene glycol monobutyl ether,triethylene glycol monobutyl ether, propylene glycol, and other watermiscible organic solvents, an inorganic salt, sodium chloride or anonionic or anionic surfactant.
 18. A method to improve ICI viscosity ofan aqueous composition comprising: providing an effective amount of aviscosity regulating composition to an aqueous composition, theviscosity regulating composition comprises the viscosity regulatingcomposition according to claim 1, wherein the ICI viscosity of theaqueous composition ranges from 0.5 to 5.0 Poise.
 19. A method ofmanufacturing a viscosity regulating composition according to claim 1comprising the steps of: forming a solvent-free melt of (i) analkoxylated polyhydroxyl segment, having the formula [M]-(AO)_(n) having3 to 6 reactive hydroxyl linking groups, n ranges from 3 to 6, amolecular weight ranging from 10,000 g/mole to 50,000 g/mole, and (ii)an alkoxylated aliphatic end segment or alkoxylated aromatic endsegment, having the formula (AO)—R and a reactive hydroxyl linking groupand a molecular weight ranging from 2,000 g/mole to 10,000 g/mole;contacting the solvent-free melt with aliphatic linking segments oraromatic linking segments, L, each having at least two hydroxyl reactivelinking groups under conditions sufficient to form a compositioncomprising a mixture of a branched polymer having the formula[M]-[(AO)-L-(AO)—R]_(n) and a polymer having the formulaR-(AO)-L-(AO)—R, wherein the mole ratio of the alkoxylated polyhydroxylsegment to the alkoxylated aliphatic end segment or alkoxylated aromaticend segment ranges from 1:3 to 1:30; 1:3 to 1:14; 1:9 to 1:22.
 20. Amethod of manufacturing a viscosity regulating composition according toclaim 1 comprising the steps of: forming a solvent-free melt of (i) analkoxylated polyhydroxyl segment, having the formula [M]-(AO)_(an)having 3 to 6 reactive hydroxyl linking groups, n ranges from 3 to 6, amolecular weight ranging from 1,000 g/mole to 10,000 g/mole, and (ii) analkoxylated aliphatic end segment or alkoxylated aromatic end segment,having the formula (AO)—R, a reactive hydroxyl linking group and amolecular weight ranging from 500 g/mole to 2,000 g/mole; contacting thesolvent-free melt with ethylene oxide, propylene oxide or combinationthereof under conditions sufficient to form a mixture of an alkoxylatedpolyhydroxyl segment having a molecular weight ranging from 10,000g/mole to 50,000 g/mole and an alkoxylated aliphatic end segment oralkoxylated aromatic end segment having a molecular weight ranging from2,000 g/mole to 10,000 g/mole; contacting the solvent-free melt withaliphatic linking segments or aromatic linking segments, L, each havingat least two hydroxyl reactive linking groups under conditionssufficient to form a composition comprising a mixture of a branchedpolymer having the formula [M]-[(AO)-L-(AO)—R]_(n) and a polymer havingthe formula R-(AO)-L-(AO)—R, wherein the mole ratio of the alkoxylatedpolyhydroxyl segment to the alkoxylated aliphatic end segment oralkoxylated aromatic end segment ranges from 1:3 to 1:30; 1:3 to 1:14;1:9 to 1:22.
 21. A method of manufacturing a viscosity regulatingcomposition according to claim 1 comprising the steps of: reacting atleast two moles of alkoxylated aliphatic end segment or alkoxylatedaromatic end segment, having the formula (AO)—R and a reactive hydroxyllinking group and a molecular weight ranging from 2,000 g/mole to 10,000g/mole, with an aliphatic linking segments or aromatic linking segments,L, having at least two hydroxyl reactive linking groups under conditionssufficient to form a composition having a formula of R-(AO)-L-(AO)—R;adding the composition having a formula of R-(AO)-L-(AO)—R to a solventfree melt of (i) an alkoxylated polyhydroxyl segment, having the formula[M]-(AO)_(n) having 3 to 6 reactive hydroxyl linking groups, n rangesfrom 3 to 6, a molecular weight ranging from 10,000 g/mole to 50,000g/mole, and (ii) an alkoxylated aliphatic end segment or alkoxylatedaromatic end segment, having the formula (AO)—R and a reactive hydroxyllinking group and a molecular weight ranging from 2,000 g/mole to 10,000g/mole; contacting the solvent-free melt with aliphatic linking segmentsor aromatic linking segments, L, each having at least two hydroxylreactive linking groups under conditions sufficient to form acomposition having the formula branched polymer having the formula[M]-[(AO)-L-(AO)—R]_(n), wherein the mole ratio of the alkoxylatedpolyhydroxyl segment to the alkoxylated aliphatic end segment oralkoxylated aromatic end segment ranges from 1:3 to 1:30; 1:3 to 1:14;1:9 to 1:22.